CN111230352B - Preparation method and application of nano metal soldering paste with silver-tin core-shell structure - Google Patents
Preparation method and application of nano metal soldering paste with silver-tin core-shell structure Download PDFInfo
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- CN111230352B CN111230352B CN202010059423.6A CN202010059423A CN111230352B CN 111230352 B CN111230352 B CN 111230352B CN 202010059423 A CN202010059423 A CN 202010059423A CN 111230352 B CN111230352 B CN 111230352B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
- B23K35/0244—Powders, particles or spheres; Preforms made therefrom
- B23K35/025—Pastes, creams, slurries
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K1/00—Soldering, e.g. brazing, or unsoldering
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K2101/00—Articles made by soldering, welding or cutting
- B23K2101/36—Electric or electronic devices
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K2101/00—Articles made by soldering, welding or cutting
- B23K2101/36—Electric or electronic devices
- B23K2101/40—Semiconductor devices
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- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
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Abstract
The invention provides a preparation method and application of nano metal soldering paste with a silver-tin core-shell structure, which comprises the following steps of pretreating nano silver; preparing sodium borohydride reducing solution; the tin is coated with nano silver, namely the nano metal soldering paste with the silver-tin core-shell structure. The sintering temperature of the tin-silver nuclear shell layer composite metal is lower than that of the nano silver, and the service temperature of the tin-silver nuclear shell layer composite metal is higher than that of the tin metal soldering paste; the cost price of the sintering paste material is reduced integrally; the electromigration phenomenon of silver is reduced, and the use quality of the soldering paste is improved; the strength of the interconnection material joint can reach more than 25 MPa.
Description
Technical Field
The invention relates to the technical field of preparation of composite nano materials, in particular to a preparation method and application of nano metal soldering paste with a silver-tin core-shell structure.
Background
Currently, with the development of power semiconductor devices, the characteristic size of the semiconductor device pushes the package size to become smaller and smaller. Meanwhile, people have higher and higher performance requirements on power electronic devices. Thus, wide bandgap semiconductor devices that are high voltage, high temperature, and high power resistant, such as silicon carbide and gallium nitride based devices, continue to emerge. The semiconductor device has the characteristics of higher blocking voltage, low on-state specific resistance, low switching loss, high temperature resistance, radiation resistance and the like, and still has very good conversion characteristic and working capacity at the working temperature of 250 ℃. Therefore, to meet the demanding requirements of future product applications, packaging technology must have a good match of electrical, thermal and mechanical properties, as well as excellent reliability.
However, alloy solder or conductive paste is commonly used as the lead-free interconnection material, but most of the lead-free solder and conductive paste have reliable operation temperature far below 200 ℃. This severely limited the application of wide bandgap semiconductor power electronics. Therefore, there is a need to develop new lead-free interconnect materials and interconnect technologies for high power wide bandgap semiconductor devices that can be used at high temperatures. As a new interconnection material, nano silver solder paste has attracted more and more attention due to its advantages of excellent electrical and thermal conductivity, high melting point (960 c for bulk silver), and the like. However, the high cost of silver and the high sintering temperature place significant limitations on such sintered materials. Tin metal materials are the most widely used interconnection materials in traditional electronic packaging, however, with the development of the electronic industry and the continuous development of high temperature resistant devices and chips, the development of tin is limited by the lower sintering temperature and the service temperature of tin.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a preparation method of a nano metal soldering paste with a silver-tin core-shell structure, aiming at solving the problems of high cost, higher sintering temperature and low service temperature of a soldering paste sintering material of nano silver prepared by the prior method, and specifically comprising the following steps:
s1, ultrasonically washing nano silver by using deionized water;
s2, adding the nano silver powder washed by deionized water into acetone, performing ultrasonic treatment to obtain an acetone solution containing silver powder, and naturally volatilizing the acetone in the acetone solution containing silver powder to obtain the dried nano silver powder to be coated;
s3, preparing the concentration of 1 multiplied by 10-2mol/L-2×10-2mol/L sodium borohydride reducing solution;
s4, adding the nano silver powder to be coated into the sodium borohydride reducing solution by using a magnetic stirrer at a stirring speed of 300-400 r/min, stirring for 10-25min, and dropwise adding a divalent tin ion solution (Sn (OH) under the condition of constant rotating speed2) Stopping stirring when the nano silver is changed from black to silver to obtain a tin-coated nano silver solution;
and S5, drying the tin-coated nano silver solution to obtain the nano metal soldering paste with the silver-tin core-shell structure.
The melting point (230 ℃) of the tin is slightly lower than the sintering temperature of the nano-silver(280 ℃), during actual use, with the increase of temperature, organic substances in the interconnection material are reduced continuously, tin at the outermost layer starts to melt to form a liquid state, and the diffusion bonding of particles with the higher-melting-point nano silver is accelerated to form a compact structure. And the final sintering temperature is about 230-240 ℃. And due to Ag formed during sintering3Sn reduces electromigration during operation of the interconnect material. Ag formed by reaction of Ag with Sn atoms3Sn, and Ag3Sn may act to hinder silver electromigration.
Preferably, the ultrasonic washing condition in S1 is 20K-40KHz at room temperature, and the washing time is 15min-30 min.
Preferably, the ultrasonic treatment in S2 is carried out at the temperature of 25-50 ℃ and the treatment time of 20K-40KHz is 10-15 min.
Preferably, the sodium borohydride reducing solution in S3 is prepared by the following method: adding sodium hydroxide into deionized ice water, adjusting the pH value of the solution to 11-12, and then adding sodium borohydride to obtain a sodium borohydride reducing solution.
The sodium borohydride has strong reduction performance, is stable to moisture and oxygen in the air, is easy to operate and treat, and is suitable for industrial scale.
Preferably, the drying conditions in S5 are: the temperature is 90-100 ℃, and the time is 6-10 h.
A sintering method of silver-tin core-shell structure nano metal soldering paste prepared by the method comprises the following steps:
s1, coating the nano metal soldering paste on a substrate;
s2, chip bonding;
and S3, sintering, cooling and finishing the preparation of the device.
The silver-tin core-shell structure nano metal soldering paste can be applied to the technical fields of automobile electronics, power electronics, IGBT, wide bandgap semiconductor packaging and the like.
Preferably, the thickness of the nano metal solder paste in S1 is 25-35 um.
Preferably, the sintering condition of S3 is pressure of 10-20 MPa; the sintering process is as follows: rapidly heating to 160 deg.C, and maintaining the constant temperature for 15min-30 min; rapidly heating to 180 deg.C, and maintaining the constant temperature for 15min-30 min; quickly heating to 230-250 deg.C, and holding the temperature for 50-80 min.
If the chip is small-sized, no pressurization is needed, and no inert gas protection is needed.
The sintering temperature of the nano silver is about 280 ℃, and the maximum temperature of service after the nano silver is formed into a compact structure is 960 ℃. The maximum service temperature of the tin metal is about 230 ℃.
The beneficial effects of the invention at least comprise:
1. the sintering temperature of the tin-silver nuclear shell layer composite metal is lower than that of the nano silver, and the service temperature of the tin-silver nuclear shell layer composite metal is higher than that of the tin metal soldering paste.
2. The cost price of the sintering paste material is reduced as a whole.
3. Reduce the electromigration of silver and improve the use quality of the soldering paste.
4. The strength of the joint of interconnecting material can reach 25 Mpa.
Drawings
FIG. 1 is a schematic structural diagram of silver-tin core-shell structure nano metal solder paste.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the scope of the present invention.
Example 1
(1) And (4) carrying out ultrasonic washing on the nano silver by using deionized water at room temperature for 15min at 20KHz, thus obtaining the nano silver cleaned by the deionized water.
(2) Adding the nano silver powder washed by deionized water into acetone (acetone is volatile), and treating the acetone solution containing the silver powder for 10min by using an ultrasonic cleaning machine with the temperature of 25 ℃ and the frequency of 30KHz to obtain the acetone solution containing the silver powder after ultrasonic treatment.
(3) And naturally volatilizing acetone in the acetone solution containing the silver powder at room temperature to obtain the dried silver powder to be coated.
(4) Adding sodium hydroxide into deionized ice water to obtain alkaline solution, adjusting pH to 12, adding sodium borohydride into the alkaline solution to obtain solution with concentration of 1 × 10-2And (3) mol/L sodium borohydride reducing solution.
(5) And adding the obtained dried nano silver powder to be coated into the sodium borohydride reducing solution at the stirring speed of 300r/min by using a magnetic stirrer, and stirring for 15min to obtain a nano silver solution. And drying the wet nano silver at the temperature of 90 ℃ for 6 hours to obtain the nano silver soldering paste.
The joint strength of the nano-silver soldering paste is 25-35MPA, the thermal conductivity is 110 +/-10W/mK, and the sintering temperature of the soldering paste is 250-280 ℃.
Example 2
A preferred embodiment comprises the following preparation steps:
(1) and (4) carrying out ultrasonic washing on the nano silver by using deionized water at room temperature for 15min at 20KHz, thus obtaining the nano silver cleaned by the deionized water.
(2) Adding the nano silver powder washed by deionized water into acetone (acetone is volatile), and treating the acetone solution containing the silver powder for 10min by using an ultrasonic cleaning machine with the temperature of 25 ℃ and the frequency of 30KHz to obtain the acetone solution containing the silver powder after ultrasonic treatment.
(3) And naturally volatilizing acetone in the acetone solution containing the silver powder at room temperature to obtain the dried silver powder to be coated.
(4) Adding sodium hydroxide into deionized ice water to obtain alkaline solution, adjusting pH to 12, adding sodium borohydride into the alkaline solution to obtain solution with concentration of 1 × 10-2And (3) mol/L sodium borohydride reducing solution.
(5) Adding the obtained dried nano silver powder to be coated into sodium borohydride reducing solution at a stirring speed of 300r/min by using a magnetic stirrer, stirring for 15min, and then dropwise adding a divalent tin ion solution (Sn (OH) under the condition of constant rotating speed2) And stopping stirring after the nano silver is changed into color from black to silver, so as to obtain the tin-coated nano silver solution. Wet tin-coated nano silver at 90 deg.CAnd drying for 6 hours to obtain the nano metal soldering paste with the silver-tin core-shell structure.
The nano metal soldering paste joint with the silver-tin core-shell structure has the strength of 25-30MPA, the thermal conductivity of 120 +/-10W/mK and the sintering temperature of 200-230 ℃.
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (4)
1. A preparation method of nano metal soldering paste with a silver-tin core-shell structure is characterized by comprising the following steps:
s1, ultrasonically washing nano silver by using deionized water to obtain first nano silver powder;
s2, adding the first nano silver powder into acetone, performing ultrasonic treatment to obtain an acetone solution containing silver powder, and volatilizing the acetone in the acetone solution containing silver powder to obtain a second nano silver powder to be coated after drying;
s3, preparing the concentration of 1 multiplied by 10-2mol/L-2×10-2mol/L sodium borohydride reducing solution;
s4, adding the second nano silver powder into the sodium borohydride reducing solution by using a magnetic stirrer at a stirring speed of 300-400 r/min, stirring for 10-25min, keeping the rotating speed unchanged, dropwise adding the divalent tin ion solution, and stopping stirring when the nano silver is changed from black to silver to obtain a tin-coated nano silver solution;
s5, drying the tin-coated nano silver solution to obtain nano metal soldering paste with a silver-tin core-shell structure; the strength of the nano metal soldering paste joint of the silver-tin core-shell structure is 25-30MPA, the thermal conductivity is 120 +/-10W/mK, and the sintering temperature of the soldering paste is 200-230 ℃;
the ultrasonic washing condition in the S1 is 20K-40KHz at room temperature, and the washing time is 15min-30 min;
the ultrasonic treatment in the S2 is carried out for 10-15min at the temperature of 25-50 ℃ and under the condition of 20K-40KHz treatment;
the sodium borohydride reducing solution in the S3 is prepared by the following method: adding sodium hydroxide into deionized ice water, adjusting the pH value of the solution to 11-12, and then adding sodium borohydride to obtain a sodium borohydride reducing solution;
the drying conditions in the S5 are: the temperature is 90-100 ℃, and the time is 6-10 h.
2. A sintering method of silver-tin core-shell structure nano metal solder paste prepared by the method of claim 1, which is characterized by comprising the following steps:
s1, coating the nano metal soldering paste on a substrate;
s2, chip bonding;
and S3, sintering, cooling and finishing the preparation of the device.
3. The sintering method of nano metal solder paste according to claim 2, wherein the thickness of the nano metal solder paste in S1 is 25-35 um.
4. The sintering method of nano metal solder paste according to claim 2, wherein the sintering condition of S3 is a pressure of 10 to 20 MPa; the sintering process is as follows: rapidly heating to 160 deg.C, and maintaining the constant temperature for 15min-30 min; rapidly heating to 180 deg.C, and maintaining the constant temperature for 15min-30 min; quickly heating to 230-250 deg.C, and holding the temperature for 50-80 min.
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| CN113385857A (en) * | 2021-06-15 | 2021-09-14 | 广东工业大学 | Multi-size micro-nano metal particle soldering paste in-situ interconnection process and product thereof |
| CN114049981B (en) * | 2021-11-30 | 2024-03-15 | 四川英诺维新材料科技有限公司 | Silver tin nano material conductive silver paste and application thereof to vacuum glass |
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Effective date of registration: 20230329 Address after: No. 1088, Xueyuan Avenue, Taoyuan Street, Nanshan District, Shenzhen City, Guangdong Province Patentee after: SOUTH University OF SCIENCE AND TECHNOLOGY OF CHINA Address before: Taizhou building, No. 1088, Xueyuan Avenue, Xili University Town, Nanshan District, Shenzhen City, Guangdong Province Patentee before: SHENZHEN THIRD GENERATION SEMICONDUCTOR Research Institute |